Propylene resin stabilized with a mixture of a para-tertiaryalkylphenolformaldehyde resin and an aminodithioformate



United States Patent PROPYLENE RESIN STABILIZED WITH A MIX- TURE OF A PARA-TERTIARYALKYLPHENOL- FORMALDERYDE RESIN AND AN AMXNODI- THXOFORMATE Bernard 0. Baum, Plalnlield, NJ assignor to Union Carbide Corporation, a corporat on of New York No Drawing. Filed Jan. 5, i960, Ser. No. 493. 10 Claims. (Ci-26043) This invention relates to improved propylene polymer compositions. More particularly, it relates to polypropylene having greatly increased resistance to light and thermal degradation and being substantially light in color.

Solid polypropylene is recognized in the plastics industry as possessing great commercial potential because of some advantages it has over polyethylene. For example, it has a higher melting temperature, a lower density and greater stiffness moduli than polyethylene. Polypropylene polymers can be produced in amorphous or crystalline form depending upon the catalysts employed and the reaction conditions. The highly crystalline polypropyicnes having melt indices (measured at 190' C.) within the range of from about 0.01 to about 50 are particularly suitable for use in the production of fibers, films and other extruded and molded items. These high molecular weight, highly crystalline polypropylenes are characterized by their clarity, their high toughness and strength, their good mechanical resiliency and their high stillness moduli.

Unfortunately. propylene polymers are subject to severe deterioration from the oxidative action of air at elevated temperatures. For example, fibers that are melt spun from polypropylene and have high initial strengths, 4 to 5 grams per denier, lose about 50 percent of their strength within about 50 hours after being placed in a circulating air oven at 123 0., and tend to disintegrate completely within about 100 hours to a powdery material. The stability of unstabillaed crystalline polypropylene to heat aging also varies with the amount of impurities or catalyst residue remaining in the polymer, and in certain cases, the polymer is so unstable that fibers produced therefrom dis integrate within 5 to hours at 123' C. This susceptibility of polypropylene to deteriorate under such conditions is much greater than that observed with most other high molecular weight polyoleiin resins. This can be seen when one considers that unstabilized polyethylene fibers can withstand 300 hours at 100 0. without serious loss in strength.

While it is known that small amounts of some antioxidants, for example, 4,4'-thio-bis(6-tertiarybutyl-3- methylpheaol); 2.2-bis(4-hydroxyphenyl)propane; diphenylamine; etc., can be added to polypropylenes to prevent degradative eflects during the short period the polymer is heated for melt spinning to produce fibers, it is not possible by the use of these conventional and well known anti-oxidants to prevent the oxidative degradation that occurs over prolonged exposure to air at temperatures below the melting temperature of polypropylene. For example, the inclusion in a polypropylene fiber of two percent by weight of 4.4'-thio-bis(6-tertiarybutyl-3- methylphenol), which is lmown to be one of the most effective anti-oxidants for polyethylene, increases the time of exposure at 125' 0. required to cause 50 percent less iiii 'ice

in strength from 50 hours to only about hours. It can be seen that this is still inferior to unstabilized polyethylene fibers.

Polypropylene can be stabilized against thermally induced degradation with a great variety of phenolic resins. among which are the uniquely effective p-tertiary alltyiphenolforrnaldehyde resins. The so stabilized polypropylene compositions are more resistant to air oxidation and thermal degradation during compounding and are able to endure the forming temperatures with no significant reduction of strength or electrical properties. However, relatively large concentrations, i.e., 0.1 to 1 percent are needed to provide the degree of stabilization generally required especially for fiber applications. Unfortunately, the phenolic resins impart a brownish-yellow color to the polypropylene. The higher the concentration of the phenolic resin the greater is the discoloration.

It is therefore the general object of the present invention to provide propylene resin compositions containing phenolic resin stabilizers which are even more stable toward light and thermal degradation than heretofore known and in addition are much improved with respect to color.

This general object as well as others which will be obvious from the specification and the appended claims is achieved by the compositions of the present invention which comprise a normally solid polymer of propylene, a p-tertiary-alltylphenol-formaldehyde resin, and a salt of an N-substituted amlnodithioformic acid.

The low molecular weight para-tertiaryalltylphenolformaldehyde resins suitable for use in this invention are the A-stage resins produced by the reaction of paratcrtiaryalityl-phenois with formaldehyde in the presence of a catalyst. The A-stage of a phenol-formaldehyde resin is the early stage in the production of those'thermosetting resins in which the product produced is still soluble in certain liquids and fusible. This stage in the production of thermosetting resins is distinguished from the B-stage and Gates. The B-stage is an intermediate stage in the reaction of a therrnosetting resin in which the product softens when heated and swells when in contact with certain liquids, but does not entirely fuse or dissolve. The C-stage is the final stage in the reactions of a thermosetting resin in which the material is relatively insoluble and infusible. Thermosetting resins in a fully cured state are in this stage.

The A-stage realm used as anti-oxidants in this invention are those produced by the reaction of para-tertiaryallrylphenols with formaldehyde in the presence of a suitable catalyst, such as oxalic acid, by procedures which are well known in the plastics art. Among the paratertiaryslkylpenols which can be used in producing the suitable A-stage resins by reaction with formaldehyde are the paratertiaryalitylphenols, in which the alltyl group contains from 4 to about 20 carbon atoms or more, preferably from 4 to about 10 carbon atoms, such as para-tertiarybutylphenol, para-tertiaryamylphenol, para-tertlaryheptylphenol. para-tertlarynonylphenol and the like.

illustrative of the A-stage resins that can be used to control the oxldative degradation of polypropylene are para-tcrtiarybutyiphenoHormaldehyde resin, para-tertiaryamylphenol-forma-ldchyde resin, para-tertiarynonylpbcnoiformaldehydc resin, para-tertiarydodecylphenolformaldehyde resin and the like. The resins can be prepared fromthe pure para-phenol or from a mixture of para phenol with the ortho and/or meta isomers.

However, the effectiveness of the A-stage resins as antioxidants is dependent in very large measure upon the para-tertiaryalkylphenol content in the resin. Thus, even though an A-stage resin formed from a mixture of isomeric alltylphenols having a major proportion of the para isomer is an effective constituent of the present compositions, larger quantities of the A-stage resin are needed in order to have a sufficient concentration of the para-tertiaryalkylphenol-formaldehyde resin in the polypropylene to give equivalent stabilization to that achieved when a para-tertiarybutylphenol-formaldehyde resin produced from para-tertiarybutylphenol alone is utilized. Also, mixtures of two or more para-tertiaryalltyiphenolformaldehyde resins can be employed.

The aminodithioformate compounds suitable for use in the compositions of the present invention are those which correspond to the general formula wherein M is a cation selected from the group consists of Nth". Te++++ and x is an integer having a value equal to the positive valence of M; and Am is an amino radical selected from the group consisting of (l) a dialkyl amino radical having the formula wherein R and R are each an allryl group containing from i to 6 carbon atoms, and (2) a polymethylcnc amino radical having the formula ohmsr/ wherein n has a value of from 4 to 6 inclusive.

Preferably the aminodithioformate compound is the zinc salt in which the amino group is a dialltyl amino radical, particularly the dibutyl amino radical.

illustrative of the aminodithioformate compounds suitable for use in the present invention are sodium diethylaminodithiofonnatc, selenium dimethylaminodithioi'ormate. ammonium diethylaminodithioforrnate. ammonium diisobutylaminodithioformate, zinc dlethyiaminodlthioformats, zine dimethyiaminodithioformate, zinc dlbutylsminodithioformate, piperidinium diamylamlnodithioformate, selenium piperidyldithioformate, piperidinium piperidyldithioformate, tellurlum dimethylarninodithioformats, and the like.

The aminodithloformate salts are for the most part well known chemical compounds and are commercially available. Particularly is this true of the zinc diatkylaminodithioformates. The ammonium salts, for instance. can be readily prepared by the reaction of ammonia and primary or secondary amines with carbon disuiflde. The sodium salts are obtained directly by using sodium hydroxide in the reaction between the amine and carbon disuitlde.

Propylene resin compositions having improved heat and light stability and greatly improved color are, according to this invention, those which contain from about 0.05 to about 5.0 percent by weight or greater of the A- stage para-tertisryalltylphenoldormaldehyde resin hereinbefore described based on the weight of the polypropylene present, and in combination therewith an N-substituted aminodithloformie acid salt in an amount of from about to 600%, preferably to 200%, by weight based on the weight of the phenolic resin stabilizer. The term "propylene resin" is intended to include propylene homopolymers and eopolymers of propylene and one or more ethylenically unsaturated monomers in which the content of propylene polymerized therein is percent or greater and preferably at least percent by weight.

Whereas the proportion of A-stage phenolic resin to propylene polymer and the proportion of am-inodithitfi. formate decoiorizer to A-stage phenolic resin as set fort above are satisfactory to produce a stable product having a light color suitable for all but the most unusual use requirements, it is to be understood that greater or lesser quantities of either the phenolic resin or the de colorizer can be utilized and still be within the spirit and proper scope of the invention. in a practical sense, however. greater latitude can be exercised with respect to the phenolic resin than with the aminodithioformate constituent since ratios of aminodithioformate to phenolic resin of greater than 6:1 on a weight basis do not to any large degree improve the color of the final composition.

The pnra-tertiaryaikylphcnol-formaldehyde resinaminodithioformatc stabilizer composition can be incorporated into the polypropylene by any suitable means. for example, by fluxing the polypropylene with the stabilizer composition on heated rolls, by the use of Banbury mixers, or of heated cxtrudcrs, and the like, or by the use of a solvent solution of the stabilizer.

The following examples will serve to further illustrate the present invention.

in the examples, at each occurrence the following definitions and characterizations apply: 7

Yellowness lndCX- n'lt2 ycllowness index reported is the quotient of the degree of yellowness divided by the degree of whiteness of any given polypropylene composition tested. Yellowness and whiteness are based on color reflectance measurements made on molded plaque samples by means of a spectrophotometer modified for reilcctance measurements (Beckman Model "B" abridged). The reflectance over vitrolitc. an arbitrarily chosen refiectance standard, was measured on the plaque samples at wave lengths of 550 mg and 430 mp. whiteness is based on the percentage reflectance at 550 mi and yellowness is based on the percentage reflectance at 430 mi. The yellowncss index is therefore equal to un Ina 030 ma sso miin which R is the percentage reflectance at the wave length indicated by the subscript. The smaller the quotient, the lighter the color of the composition.

Polypropylene rrsim-lhe propylene homopolymer employed is a typical normally solid polypropylene having a melt index of 3.1 decigrams per minute, a density of 0.908 gram per milliliter at 23' C. and a tensile modulus of 138,000 pounds per square inch.

MIDF (melt Index depreciation Iactor).-The ratio of melt index of polypropylene resin or resin composition after heating 15 min. at 288' C. compared to the initial melt index. The melt index determination was in accord ance with ASTM test 04238-521.

Thermal stabllity (induction period in hours in air at C.).As a measure of the thermal stability, the composition tested was compression molded into 30 mil thick plaques which were then suspended in a C. circulating air oven. Periodically the plaques were ex-' amined and subjected to a manually applied bending force. The plaques either sustained the applied force without discernible ill-effect or crumbled into small powdery fragments. The plaques did not exhibit any inbetween behavior. The time period during which the plaque couiigd resist the applied force is called the induction per Phenolic stabilizer. An A-stage para-ttertiaryarnylphenol-formaldehyde resin having a softening point at 185' F. prepared by the oxalic acid catalyzed condensation of paratertiaryamylphenol and formaldehyde under reflux conditions. The condensation product mass was then vacuum distilled to remove formed water, unrcacted phenol and low molecular weight condensation products, and thereafter cooled and ground.

Weathering Resistance (hours to embrittiement).This roperty is indicative of the resistance of the polypropylne resins or compositions to the eil'ects of typical climatic conditions. The sample is subjected to an accelerated program of exposure to light and water in the apparatus and according to the standard procedure specified in AST M test method D-822-57T.

EXAMPLES 1-8 The synergistic stabilizing action of an arninodithioformate and a phenolic resin stabilizer was demonstrated by preparing a series of polypropylene compositions, some of which contained both an aminodithlot'ormato and n phenolic resin, and some of which contained only the aminodithiot'ormate. The compositions were prepared by admixing the modifiers with the polypropylene immediately after the polypropylene had been fluxed and sheeted on a two-roll mill at 170' C. The modifiers were thoroughly blended with the fluxed polypropylene by successively end-prising the mixture through the mill nip ten times. For control, the same polypropylene was hot processed according to the same procedure, one portion receiving no modifiers, and two portions being admixed with the phenolic resin stabilizer in amounts of 0.5 percent by weight and L percent by weight respectively. A portion of all compositions so prepared was compression molded and subjected to weathering and thermal abuse in air at 150 C. The results are reported in 6 EXAMPLE 9 Using the same procedure for combining ingredients as in Examples 1-8, a series of polypropylene compositions containing various amounts of zinc diethyiarninodithioformate and/or phenolic resin stabilizer were prepared and tested for color and thermal stability as hereinbefore described. The results are shown in tabular form below.

Table II Promoter Phenolic stabi- None Zinc dlethylamlnodlthiotormate llser, cone (wt. Stabll- MID F Cone. Stabll- MID F percent Color b [big at at 288' (wt. Color h lg at at 288 l C. O. por- 1 C. C.

ornt

.... 0.89 4 15 0.1 7 0.0 0.5 0.41 12 1.8 1.0 20 1.5 0. b l. 4 0. i 0.04 40 l. 3 0.5 0.5 0.57 04 1.3 1.0 1.3 2.0 0.85 100 1.5

l Based on the weight oi polypropylene. Yellowneaa index.

it can be seen from the data in Table II that the phenolic resins, when used alone, stabilize polypropylene against air oxidation at 150' C., but cause pronounced yellowing, and that both the stabilizing action and yellowing become greater with increasing phenolic resin concentration. it is also apparent that the aminodithioformates when used alone, have only a small stabilizing effect on polypropylene in air at 150 C., and, it anything, a slight Table 1 below. adverse eil'ect on color.

Table I Thermal Weathering stability Composition resistance (Induction (hrs. to tied at embrlttle- C. in

meat) air, hrs.)

Unmodified pol lens 200 0 l'olyprorylr'no [I i l t phenolic min stshllser. 500 82 Polypropylene plus 1. phenolic resin stahlllser 7504.000 48 Ex. Polypropylene Addttlm 800 12 osst phenolic summer... into M 500 12 2 .....d0 2 16. M 3 .....d0 7 a t do a tisans-traits u no .8 sodium 5 snhdo {g m I'M 6 do {0.5 plpertd 126 l) s s a a n n 5 itch... 1,500 6'1 7 {0% selenium tllmethyiemlnodithlotonnah l2 0 I selenium dlmethylsmtnodlthlolormste plus 0.8% phenolic stsbil- 78 set. a d {0.5 tellurtutn d lethylsmlaod lthtotonnats to u 0.1: tsllurium dtethylamlnodlthlolormsto plus 0.5% phenolic stabil- H ser it is readily apparent from the data oi Table 1 that each EXAMPLE IQ of the stabilizing modifiers used above improve the weath- 7n ering resistance and the thermal stability, but that when the phenolic resin stabilizer and the aminodithloiormate are used in combination, much greater stability is imparted to the composition than would result from merely adding the improvement credited to each.

The effect of concentration of additives in the poly-- propylene compositions of this invention were determined by preparing a series of compositions according to the procedure of Examples 1-8 containing various'amounls of phenolic resin stabilizer and/or zinc dimethylaminodithloiormate, and testing the compositions thus obtained 7 for resistance toward cmbrittlement in air at "150 C. Thle formulations and results are set forth in Table Ill be ow.

The contribution of the aminodithiolormate is surprising in that it does not. by itself, elicctively stabilize polypropylene against cmbrittlcment in air at 150' C., but it greatly improves the ability of the phenolic resin to do so.

EXAMPLE ii A styrene-propylene eopolymer having a melt index of about 0.03 and containing an intcrpolymerined styrene to propylene ratio of 18:82 was blended with 0.5 percent by weight of the para-tertiaryamylphenol-formaldehyde resin stabilizer oi Examples 1-8. A portion of this blend was further blended with zinc diethylaminodithiotormate in an amount of 0.5 percent by weight of the over-all composition. Each of the two compositions was compression molded and yellowness index determinations made. The yellowness index of the copolymer composition containing only the phenolic resin stabilizer was found to be 0.47. fire ycllowness index of the composition containing both the phenolic resin stabilizer and the zinc diethylaminodithiol'ormate was found to be 0.3l.

The polypropylene compositions of the present invention find particular utility, because of their resistance to oxidation degradation. as extruded or spun textile fibers and yarns. These compositions find additional utility in the form of films and sheets suitable for packaging, and in the form of a wide variety of extruded and molded articles.

The compositions can also include conventional additives such as colorants. lubricants. slip agents, plasticizers, tillers and the like and can be admixed with other polymeric materials.

What is claimed is:

l. A propylene resin composition having improved stabillty toward heat and light induced molecular degradation which comprises a normally solid propylene polymer containing at least 50 percent by weight of propylene polymerized therein, a stabilizing amount of an A-stage para-tcrtiaryallrylphenol-tormaldehyde resin in which the ailryl group of the para-tertiaryallrylpheaol contains from 4 to 20 carbon atoms, and an sminodithiotormate having the general formula /ii I x is an integer having a value equal to the positive valence of M; and Am is an amino radical selected from the group consisting of (l) a dialkyl amino group having the general formula wherein R and R are each an alkyl group containing from i to 6 carbon atoms, and (2) a polymethylene amino radical having the formula A (0th). N- V wherein n has a value of from 4 to 6 inclusive.

2. A stabilized propylene resin composition comprising a normally solid propylene polymer containing at least 50 percent by weight of propylene polymerized therein,

an A-stagc para-tertiaryalltylphcnoi-l'ormaldehyde resin in which the alkyl group of the parn-tcrtiaryalltylphcnol contains from 4 to 20 carbon atoms, said A-stage resin being present in an amount of from about 0.05 to about 5.0 percent by weight based on the weight of the pro pylene polymer, and an aminodithioiormate having the general t'ormuln am-c-s -rr wherein M is a cation selected from the group consisting of Na Zn", Se++++, Tc++++. Nl-ld, and

CC ll ll ll s A T Ila lh x is an integer having a value equal to the positive valence oi M; and Am is an amino radical selected from the group consisting of (l) a dialkyl amino radical having the formula llsC wherein R and R are each an alkyl group containing from 1 to 6 carbon atoms, and (2) a polymethylcne amino radical having the formula (Oils)- tiaryalkyl group of the A-stage para-tertiaryalkylphenol- 1 formaldehyde resin contains from 4 to l0carbon atoms. 4. The composition of claim 2 wherein the cation represented by M is Zn++ and the amino radical represented by Am is a dialltyl amino radical wherein each of the alkyl groups contains from 1 to 6 carbon atoms.

5. Theeomposition of claim 4 wherein the amino radical rcpreschted by Am is a diisopropyl amino radical.

6. The composition of claim 4 wherein the amino radical represented by Am is a diethyl amino radical.

7. The composition of claim 2 wherein the propylene polymer is a normally solid propylene homopolymer.

8. The composition of claim 2 wherein the propylene polymer is a eopolymer of propylene and styrene containing at least about percent by weight propylene poymerized therein.

9. A stabilized polypropylene composition comprising a normally solid propylene homopoiymer, an A-stage 9 para-tertiaryamylphenol-formaldehyde resin in an amount of from about 0.05 to about 5.0 percent by weight based on the weight of the propylene homopolyrner, and zinc diisopropylaminodithioformate in an amount of from about 10 percent to about 600 percent by weight based on the weight of the A-stage para-tertiaryalkylphenolformaldehyde resin.

10. The composition of claim 9 wherein the zinc diisopropyldithioformate is present in an amount of from about 20 to about 200 percent by weight based on the weight of the para tertiarynlkylphenol formaldehyde resin.

References Cited in the file of this patent UNITED STATES PATENTS Thomas June 27, 1939 Sparks May 6, 1941 Groff et al Apr. 23, 1957 Hawkins et a] June 2, 1959 Roberts et a1 Jan. 17, 1961 Newland et al Feb. 21, 1961 Newland et al Apr. 18, 1961 Maragliano et al Dec. 12, 1961 Schulde et al Feb. 6, 1962 

1. A PROPYLENE RESIN COMPOSITION HAVING IMPROVED STABILITY TOWARD HEAT AND LIGHT INDUCED MOLECULAR DEGRADATION WHICH COMPRISES A NORMALLY SOLID PROPYLENE POLYMER CONTAINING AT LEAST 50 PERCENT BY WEIGHT OF PROPYLENE POLYMERIZED THEREIN, A STABILIZING AMOUNT OF AN A-STAGE PARA-TERTIARYALKYLPHENOL-FORMALDEHYDE RESIN IN WHICH THE ALKYL GROUP OF THE PARA-TERTIARYALKYLPHENOL CONTAINS FROM 4 TO 20 CARBON ATOMS, AND AN AMINODITHIOFORMATE HAVING THE GENERAL FORMULA 